CN104556125B - A kind of isomorphous composite molecular screen and its preparation method and application - Google Patents
A kind of isomorphous composite molecular screen and its preparation method and application Download PDFInfo
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The present invention discloses the preparation method of a kind of composite molecular screen, including following content: (1) waterglass, sodium hydroxide, water, aluminum source mixed liquor are aged 1 ~ 72 hour at 25 ~ 100 DEG C, prepares directed agents, and in mixed liquor, the mol ratio of each material isn(Na2O):n(Al2O3):n(SiO2):n(H2O)=12~20:1:12~20:320~450；(2) directed agents that addition Y type molecular sieve and step (1) prepare in the mixed liquor of waterglass, sodium hydroxide, aluminum source and water, by gel thermostatic crystallization 12 ~ 72 hours under the conditions of 90 ~ 120 DEG C after stirring, the most cooled, washing, sucking filtration, obtain Y Y compound molecular sieve after drying, the quality of the Y type molecular sieve wherein added accounts for 40 ~ 4wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for 2 ~ 20wt% of gel rubber system gross mass.In composite molecular screen prepared by the method, the hydrothermal stability of nanoscale Y type molecular sieve is improved significantly, and composite molecular screen has and more prominent is hydrocracked performance.
Description
Technical field
The present invention relates to a kind of isomorphous composite molecular screen and its preparation method and application, relate in particular to one and have
Y-Y composite molecular screen of FAU-FAU structure and its preparation method and application.
Background technology
At present, composite molecular screen obtains the concern of increasing researcher.Various composite molecular screens are constantly synthesized
Out.MCM-41/ZSM-5 composite molecular screen as disclosed in CN1208718, micro porous molecular sieve disclosed in CN1597516 (ZSM-5,
β zeolite, modenite, zeolite L, MCM-22, ZSM-35) and mesopore molecular sieve (MCM-41) composite molecular screen, CN1686800
Disclosed ZSM-22/ZSM-23 composite molecular screen, ZSM-35/MCM-22 composite molecular screen disclosed in CN101003379,
ZSM-5/ mordenite composite molecular sieve disclosed in CN101091920, ZSM-5/SAPO-5(disclosed in CN101279288 or
AlPO4-5) composite molecular screen, the composite molecular screen of the nucleocapsid structure that (Chem Mater 2006,18,4959-4966) reports
Silicalite-1/MFI etc..
Y type molecular sieve is mutually communicated along three crystalline axis direction by twelve-ring by octahedral molecular sieve cage and is formed,
Being a kind of excellent catalyst activity component, not only cracking activity is high, and selectivity is good.Therefore the discovery of Y type molecular sieve and
Use, at catalytic field, there is epoch-making meaning.Owing to high silica alumina ratio Y type molecular sieve has good hydrothermal stability and acid
Stability, therefore it has played not in the catalytic cracking of PETROLEUM PROCESSING and during being hydrocracked etc. as a kind of catalysis material
Alternative effect.
Modified work currently, with respect to Y type molecular sieve has obtained the extensive concern of numerous scientific research personnel.Y type molecular sieve
Studying in addition to acid, alkali and the hydrothermal treatment consists modification except carrying out routine, the complex technique about Y type molecular sieve have also been obtained extensively
General concern.CN200610048273.9 discloses a kind of composite molecular screen using high-Si Y-type molecular sieve to synthesize high silicon, should
Composite molecular screen organically combines Y type molecular sieve and the feature of Beta molecular sieve, and prepared composite not only has high-silicon Y-shaped
Hydrothermal stability that molecular sieve is good and absolute acid stability, also have the good heat of Beta molecular sieve and hydrothermal stability simultaneously, suitable
The acidity of degree and absolute acid stability and hydrophobic properties, show the performance of excellence in the course of reaction such as being hydrocracked.
Meanwhile, the synthesis about nano Y-shaped molecular sieve is also paid close attention to by big vast researcher, but nanometer Y of synthesis
Type hydrothermal stability of molecular sieve is poor, and in hydrothermal treatment process, crystal duct topological structure is subsided completely.Therefore, nano Y-shaped point
Son sieve cannot be widely popularized in actual applications.
Summary of the invention
For the deficiencies in the prior art, the present invention provide a kind of Y-Y isomorphous composite molecular screen with FAU-FAU structure and
Its preparation method and application.The hydrothermal stability of the nanoscale Y type molecular sieve in this composite molecular screen is improved significantly, compound
Molecular sieve has and more prominent is hydrocracked performance.
The preparation method of a kind of composite molecular screen, comprises the steps:
(1) waterglass, sodium hydroxide, water, aluminum source mixed liquor are aged 1 ~ 72 hour, preferably 45 ~ 80 at 25 ~ 100 DEG C
Being aged 12 ~ 60 hours at DEG C, prepare directed agents, in mixed liquor, the mol ratio of each material isn(Na2O):n(Al2O3):n(SiO2):n(H2O)=12 ~ 20:1:12 ~ 20:320 ~ 450, preferred molar ratio isn(Na2O):n(Al2O3):n(SiO2):n(H2O)=14~18:
1:15~18:350~430；
(2) in the mixed liquor of waterglass, sodium hydroxide, aluminum source and water, add Y type molecular sieve and prepared the leading of step (1)
By gel thermostatic crystallization 12 ~ 72 hours under the conditions of 90 ~ 120 DEG C after agent, stirring, preferably under the conditions of 95 ~ 110 DEG C, constant temperature is brilliant
Changing 36 ~ 60 hours, in gel, in addition to the Y type molecular sieve added, the mol ratio of each material isn(NaOH):n(Al2O3):n(SiO2):n(H2O)=13 ~ 16:1:18 ~ 30:480 ~ 660, preferablyn(NaOH):n(Al2O3):n(SiO2):n(H2O)=14~15.5:1:20~
26:500 ~ 620, the most cooled, washing, sucking filtration, obtain Y-Y composite molecular screen after drying, the Y type molecular sieve wherein added
Quality accounts for 4 ~ 40wt% of gel rubber system gross mass, preferably 8 ~ 30wt%, and the quality of the directed agents of addition accounts for gel rubber system gross mass
2 ~ 20wt%, preferably 5 ~ 10wt%.
In the inventive method step 1, described aluminum source includes aluminum chloride, aluminum sulfate, aluminum nitrate, sodium aluminate etc., preferably aluminum
Acid sodium.
In the inventive method step (2), the Y type molecular sieve of described addition is sodium form.Silicon oxide/the oxidation of Y type molecular sieve
Al mole ratio is 4.2 ~ 6.5, and grain size is 0.5 ~ 1.0 m, and specific surface area is 750 ~ 900m2/ g, pore volume is 0.33 ~ 0.40ml/
G, average pore size is 1.5 ~ 2.0nm；Preferential oxidation silicon/alumina molar ratio is 4.8 ~ 5.5, and grain size is 0.6 ~ 0.8 m, compares table
Area is 850 ~ 880m2/ g, pore volume is 0.36 ~ 0.40ml/g, and average pore size is 1.7 ~ 1.9nm.
A kind of composite molecular screen using said method to prepare, without stray crystal in described composite molecular screen, has core-shell type
Structure, shell is for having nano level Y type molecular sieve, and nano level Y type molecular sieve weight content is 50 ~ 85wt%, compound molecule
The silica alumina ratio of sieve is 4.9 ~ 6.1, and specific surface area is 680 ~ 850m2/ g, pore volume 0.28 ~ 0.35ml/g, average pore size is 1.5 ~
2.0nm, degree of crystallinity is 90 ~ 98%.
Composite molecular screen prepared by the said method application in preparing hydrocracking catalyst, in hydrocracking catalyst
The weight content of composite molecular screen is 20 ~ 50wt%, the weight content of activity component metal molybdenum (Mo) and nickel (Ni) is 7.0 ~
9.0wt% and 2 ~ 3wt%.
The inventive method uses hydrothermal synthesis method to prepare the Y-Y type composite molecular screen with shell layered structure, and this is combined
The hydrothermal stability with nano level Y type molecular sieve in molecular sieve shell is strengthened, and composite molecular screen is through hydro-thermal
Degree of crystallinity after process remains to reach before treatment more than 90%, the most close with oarse-grained Y type molecular sieve.Use this to be combined
The Y type molecular sieve cracking activity comparing routine of the hydrocracking catalyst that system with molecular sieve for preparing is standby is further enhanced.
Accompanying drawing explanation
Fig. 1 is the composite molecular screen XRD diffraction pattern of the embodiment of the present invention 1 synthesis, it can be seen that sintetics belongs to FAU
Structure, does not has other crystalline phase.
Detailed description of the invention
Further illustrate the preparation process of the present invention below in conjunction with embodiment, but following example are not constituted side of the present invention
The restriction of method.Preparation process all uses and adds the conventional Y type molecular sieve with following character: grain size is 0.5 m, specific surface
Amass as 800m2/ g, pore volume is 0.38ml/g, and average pore size is 1.8nm.
Embodiment 1
Preparation directed agents.Under conditions of stirring, successively waterglass, sodium hydroxide, water and aluminum source are joined in beaker,
After stirring, load in rustless steel synthesis reactor and be aged 48 hours at 50 DEG C, obtain directed agents.In mixture, each material rubs
You are at ration(Na2O):n(Al2O3):n(SiO2):n(H2O)=16: 1:15.5:360。
Prepare composite molecular screen.Under conditions of stirring, successively waterglass, sodium hydroxide, aluminum source and water are joined burning
In Bei, then joining in solution by the desired amount of Y type molecular sieve (mol ratio of silicon oxide and aluminium oxide 5.2), stirring is all
Add directed agents after even, after stirring 1.5 hours, gel loaded in stainless steel cauldron thermostatic crystallization 48h under the conditions of 100 DEG C,
Cooling, washing, sucking filtration, it is dried to obtain Y-Y composite molecular screen.The quality of Y type molecular sieve powder accounts for gel rubber system gross mass
12%；The mol ratio of each component (except Y type molecular sieve) of the mixture of synthesis composite molecular screen is:n(NaOH):n(Al2O3):n
(SiO2):n(H2O)= 14.4:1:25:560；The consumption of directed agents is the 6wt% of gel rubber system gross mass.The property of composite molecular screen
Matter is as shown in table 1.
Embodiment 2
Preparation directed agents.Under conditions of stirring, successively waterglass, sodium hydroxide, water and aluminum source are joined in beaker,
After stirring, load in rustless steel synthesis reactor and be aged 18 hours at 60 DEG C, obtain directed agents.In mixture, each material rubs
You are at ration(Na2O):n(Al2O3):n(SiO2):n(H2O) =15:1:17:380。
Prepare composite molecular screen.Under conditions of stirring, successively waterglass, sodium hydroxide, aluminum source and water are joined burning
In Bei, then joining in solution by the desired amount of Y type molecular sieve (mol ratio of silicon oxide and aluminium oxide 6.2), stirring is all
Add directed agents after even, after stirring 1 hour, gel is loaded in stainless steel cauldron thermostatic crystallization 24h under the conditions of 110 DEG C, cold
But, washing, sucking filtration, it is dried to obtain Y-Y composite molecular screen.The quality of Y type molecular sieve powder accounts for the 26% of gel rubber system gross mass；
The mol ratio of each component (except Y type molecular sieve) of the mixture of synthesis composite molecular screen is:n(NaOH):n(Al2O3):n
(SiO2):n(H2O)= 15:1:23:550；The consumption of directed agents is the 8wt% of gel rubber system gross mass.The character of composite molecular screen
As shown in table 1.
Embodiment 3
Preparation directed agents.Under conditions of stirring, successively waterglass, sodium hydroxide, water and aluminum source are joined in beaker,
After stirring, load in rustless steel synthesis reactor and be aged 56 hours at 45 DEG C, obtain directed agents.In mixture, each material rubs
You are at ration(Na2O):n(Al2O3):n(SiO2):n(H2O) =17:1:16:420。
Prepare composite molecular screen.Under conditions of stirring, successively waterglass, sodium hydroxide, aluminum source and water are joined burning
In Bei, then joining in solution by the desired amount of Y type molecular sieve (mol ratio of silicon oxide and aluminium oxide 4.8), stirring is all
Add directed agents after even, after stirring 1 hour, gel is loaded in stainless steel cauldron thermostatic crystallization 60h under the conditions of 100 DEG C, cold
But, washing, sucking filtration, it is dried to obtain Y-Y composite molecular screen.The quality of Y type molecular sieve powder accounts for the 22% of gel rubber system gross mass；
The mol ratio of each component (except Y type molecular sieve) of the mixture of synthesis composite molecular screen is:n(NaOH):n(Al2O3):n
(SiO2):n(H2O)= 14.5:1:21:520；The consumption of directed agents is the 5wt% of gel rubber system gross mass.The property of composite molecular screen
Matter is as shown in table 1.
Embodiment 4
Preparation directed agents.Under conditions of stirring, successively waterglass, sodium hydroxide, water and aluminum source are joined in beaker,
After stirring, load in rustless steel synthesis reactor and be aged 24 hours at 70 DEG C, obtain directed agents.In mixture, each material rubs
You are at ration(Na2O):n(Al2O3):n(SiO2):n(H2O) =15:1:16:360。
Prepare composite molecular screen.Under conditions of stirring, successively waterglass, sodium hydroxide, aluminum source and water are joined burning
In Bei, then joining in solution by the desired amount of Y type molecular sieve (mol ratio of silicon oxide and aluminium oxide 5.1), stirring is all
Add directed agents after even, after stirring 1 hour, gel is loaded in stainless steel cauldron thermostatic crystallization 36h under the conditions of 110 DEG C, cold
But, washing, sucking filtration, it is dried to obtain Y-Y composite molecular screen.The quality of Y type molecular sieve powder accounts for the 18% of gel rubber system gross mass；
The mol ratio of each component (except Y type molecular sieve) of the mixture of synthesis composite molecular screen is:n(NaOH):n(Al2O3):n
(SiO2):n(H2O)= 14.5:1:25:515；The consumption of directed agents is the 6wt% of gel rubber system gross mass.The property of composite molecular screen
Matter is as shown in table 1.
Embodiment 5
Preparation directed agents.Under conditions of stirring, successively waterglass, sodium hydroxide, water and aluminum source are joined in beaker,
After stirring, load in rustless steel synthesis reactor and be aged 24 hours at 60 DEG C, obtain directed agents.In mixture, each material rubs
You are at ration(Na2O):n(Al2O3):n(SiO2):n(H2O) =16:1:16:410。
Prepare composite molecular screen.Under conditions of stirring, successively waterglass, sodium hydroxide, aluminum source and water are joined burning
In Bei, then joining in solution by the desired amount of Y type molecular sieve (mol ratio of silicon oxide and aluminium oxide 6.2), stirring is all
Add directed agents after even, after stirring 1.5 hours, gel loaded in stainless steel cauldron thermostatic crystallization 60h under the conditions of 100 DEG C,
Cooling, washing, sucking filtration, it is dried to obtain Y-Y composite molecular screen.The quality of Y type molecular sieve powder accounts for gel rubber system gross mass
10%；The mol ratio of each component (except Y type molecular sieve) of the mixture of synthesis composite molecular screen is:n(NaOH):n(Al2O3):n
(SiO2):n(H2O)= 15:1:22:600；The consumption of directed agents is the 8wt% of gel rubber system gross mass.The character of composite molecular screen
As shown in table 1.
Comparative example 1
The preparation process of nano Y-shaped molecular sieve.
The preparation of directed agents: pressn(Na2O):n(SiO2):n(Al2O3):n(H2O)=16:16:1:210, after aging 18h, drips
Enter sulfuric acid solution, form gel, be configured ton (Na2O):n(SiO2):n(Al2O3):n(H2O)=7.8:16:1:400, loads anti-
In answering still, putting into calorstat crystallization 8h respectively at 90 DEG C, product is through sucking filtration, washing, and 120 DEG C are dried.Obtain nano Y-shaped molecule
Sieve.The character of molecular sieve is as shown in table 1.
Table 1
| Sequence number | Specific surface (m2/g) | Pore volume (ml/g) | Nano molecular sieve content (%) | Silica alumina ratio | Degree of crystallinity (%) |
| Y | 885 | 0.31 | 0 | 4.8 | 97 |
| Comparative example | 892 | 0.39 | 100 | 4.9 | 28 |
| Embodiment 1 | 743 | 0.39 | 76 | 5.1 | 96 |
| Embodiment 2 | 871 | 0.43 | 55 | 5.7 | 94 |
| Embodiment 3 | 844 | 0.41 | 66 | 5.0 | 94 |
| Embodiment 4 | 805 | 0.40 | 72 | 5.1 | 93 |
| Embodiment 5 | 714 | 0.32 | 83 | 5.3 | 93 |
Composite molecular screen is as the application of catalyst carrier:
Ion exchanges: in the composite molecular screen washing extremely Y type molecular sieve used and embodiment and comparative example prepared
Property, dry, then under 80 DEG C of water bath condition, carry out ion exchange with 1mol/L ammonium nitrate, make sodium oxide content be less than 0.5%,
Washing, dries, in 550 DEG C of roasting 3h, obtains hydrogen type molecular sieve.
Hydrothermal treatment consists: constant temperature processes 2h under the conditions of hydrothermal temperature is 550 DEG C respectively by hydrogen type molecular sieve, obtains at hydro-thermal
Molecular sieve after reason.
Prepared by catalyst: prepare certain density ammonium molybdate solution and nickel nitrate solution, in sequence, respectively to it
Incipient impregnation, is dried in 120 DEG C, 500 DEG C of roasting 3h, obtains, containing Mo 8.0%, the catalyst of Ni 2.4%, tabletting, grinding, sieve
The granule dividing 40～60 mesh is standby.
Evaluating catalyst condition: at reaction temperature 250 DEG C, volume space velocity 1.5h-1, hydrogen to oil volume ratio 1000:1, reaction pressure
Under the operating condition of power 3.0MPa, the n-octane hydrocracking reactivity worth of catalyst is investigated.
In hydrocracking reaction, normal octane is before skeleton C-C bond fission, and the side chain of generation is the most, carbon middle-of-chain
The probability that position carries out β-cleavage reaction is the biggest, causes the content of iso-butane in product the highest, and therefore we select iso-butane
Productivity represent the cracking performance of catalyst.
Catalyst catalytic performance test in n-octane hydrocracking reacts is in a set of continuous flowing fixed bed WF-
Carry out on 9100 II type micro-reaction equipments, with micro-amounts of liquids dosing pump, normal octane is squeezed into vaporizer, be sufficiently mixed with hydrogen
Rear entrance reactor.Reactor is φ=10mm stainless steel tube, and the catalyst amount of filling out is 10mL, is placed in the constant temperature zone of heating furnace,
Its top and the bottom are filled by quartz sand, and reactor gateway graphite gasket seals.Catalyst use before normal pressure in the reactor
Lower with containing H2Mixed gas (the 10%H of S2S+90%H2) vulcanize 3h in 300 DEG C.Product passes through counterbalance valve blood pressure lowering, by air
Reactant is delivered to the GC-8A gas chromatograph of Shimadzu Corporation of Japan production and is carried out on-line analysis by the six-way valve sampling driven.Color
Spectrum post is capillary column, and specification is 50m × 0.20mm × 0.33 μm, and detector is flame ionization ditector, and column temperature is permanent
Temperature 70 DEG C, detector temperature 210 DEG C, injector temperature 210 DEG C, carrier gas is high-purity N2, split ratio is 110:1, and tail blows N2It is 110
mL/min.Evaluation result is as shown in table 2.
Table 2
| Carrier | Conversion ratio (%) | Cleavage rate (%) | i-C4(%) |
| Conventional Y molecular sieve | 18.2 | 14.6 | 22.5 |
| Comparative example 1 prepares nano molecular sieve | 25.4 | 22.4 | 23.3 |
| Embodiment 1 prepares composite molecular screen | 58.8 | 56.4 | 34.5 |
| Embodiment 2 prepares composite molecular screen | 79.9 | 77.8 | 41.1 |
Claims (10)
1. the preparation method of a composite molecular screen, it is characterised in that comprise the steps:
(1) waterglass, sodium hydroxide, water, aluminum source mixed liquor are aged 1 ~ 72 hour prepared directed agents, mixed liquor at 25 ~ 100 DEG C
In the mol ratio of each material ben(Na2O):n(Al2O3):n(SiO2):n(H2O)= 12~20:1:12~20:320~450；
(2) guiding that addition Y type molecular sieve and step (1) prepare in the mixed liquor of waterglass, sodium hydroxide, aluminum source and water
Agent, by gel thermostatic crystallization 12 ~ 72 hours under the conditions of 90 ~ 120 DEG C after stirring, each in addition to the Y type molecular sieve added in gel
The mol ratio of material isn(NaOH):n(Al2O3):n(SiO2):n(H2O)=13 ~ 16:1:18 ~ 30:480 ~ 660, then through cold
But, washing, sucking filtration, obtaining Y-Y composite molecular screen after drying, the quality of the Y type molecular sieve wherein added accounts for the total matter of gel rubber system
4 ~ 40wt% of amount, the quality of the directed agents of addition accounts for 2 ~ 20wt% of gel rubber system gross mass.
Method the most according to claim 1, it is characterised in that: the aluminum source described in step (1) includes aluminum chloride, sulphuric acid
Aluminum, aluminum nitrate, sodium aluminate.
Method the most according to claim 1, it is characterised in that: waterglass, sodium hydroxide, water, the mixing of aluminum source in step (1)
Liquid is aged 12 ~ 60 hours prepared directed agents at 45 ~ 80 DEG C.
Method the most according to claim 1, it is characterised in that: in step (1), in mixed liquor, the mol ratio of each material isn
(Na2O):n(Al2O3):n(SiO2):n(H2O)=14~18:1:15~18:350~430。
Method the most according to claim 1, it is characterised in that: by gel 95 ~ 110 DEG C of conditions after step (2) stirs
Lower thermostatic crystallization 36 ~ 60 hours.
Method the most according to claim 1, it is characterised in that: each in addition to the Y type molecular sieve added in gel in step (2)
The mol ratio of material isn(NaOH):n(Al2O3):n(SiO2):n(H2O)=14 ~ 15.5:1:20 ~ 26:500 ~ 620, addition
The quality of Y type molecular sieve accounts for 8 ~ 30wt% of gel rubber system gross mass, and the quality of the directed agents of addition accounts for gel rubber system gross mass
5~10wt%。
Method the most according to claim 1, it is characterised in that: the Y type molecular sieve added in step (2) is sodium form, and Y type divides
The silica/alumina molar ratio of son sieve is 4.2 ~ 6.5, and grain size is 0.5 ~ 1.0 m, and specific surface area is 750 ~ 900m2/ g, hole
Appearance is 0.33 ~ 0.40ml/g, and average pore size is 1.5 ~ 2.0nm.
8. according to the method described in claim 1 or 7, it is characterised in that: the silica/alumina molar ratio of Y type molecular sieve is
4.8 ~ 5.5, grain size is 0.6 ~ 0.8 m, and specific surface area is 850 ~ 880m2/ g, pore volume is 0.36 ~ 0.40ml/g, average pore size
It is 1.7 ~ 1.9nm.
9. one kind uses composite molecular screen prepared by the arbitrary described method of claim 1-8, it is characterised in that: described compound molecule
Without stray crystal in sieve, there is core shell structure, shell for having nano level Y type molecular sieve, nano level Y type molecular sieve weight
Content is 50 ~ 85wt%, and the silica alumina ratio of composite molecular screen is 4.9 ~ 6.1, and specific surface area is 680 ~ 850m2/ g, pore volume 0.28 ~
0.35ml/g, average pore size is 1.5 ~ 2.0nm, and degree of crystallinity is 90 ~ 98%.
10. composite molecular screen application in preparing hydrocracking catalyst described in a claim 9, it is characterised in that: add
In hydrogen Cracking catalyst, the weight content of composite molecular screen is 20 ~ 50wt%, and the weight content of activity component metal molybdenum and nickel is
7.0 ~ 9.0wt% and 2 ~ 3wt%.
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| CN109775718A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of modified Y-Y isomorphous molecular sieve and its preparation method and application |
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| CN115504481B (en) * | 2022-11-23 | 2023-04-28 | 山东齐鲁华信高科有限公司 | Preparation method of honeycomb FAU type zeolite molecular sieve |
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